Radical polymerization initiator, composition containing the same, cured product thereof, method for producing the same, and compound

文档序号：1188983 发布日期：2020-09-22 浏览：17次中文

阅读说明：本技术 自由基聚合引发剂、含有其的组合物、其固化物、其制造方法和化合物 (Radical polymerization initiator, composition containing the same, cured product thereof, method for producing the same, and compound ) 是由原宪司宫田涉入泽正福于 2019-02-15 设计创作，主要内容包括：本发明提供一种具有优异的灵敏度和在水中的溶解性的自由基聚合引发剂、含有其的组合物、其固化物、其制造方法和化合物。所述自由基聚合引发剂含有通式(A)所示的化合物(式(A)中,Z1为直接键合等,Z2表示>CR1022等,R1～R8表示氢原子等或者式(B1)(式(B1)中,L1表示直接键合等,B表示酸性基团的盐等,b表示1～10,*表示键合部位)所示的包含成盐基团的基团,R1～R8中的至少一者为包含成盐基团的基团,R101等表示氢原子等,R1～R8等所使用的烷基等中的氢原子的1个以上任选被烯属不饱和基团等取代,R1～R8等中的亚甲基的1个以上任选被双键等取代,R1、R2等邻近的基团任选相互键合而形成环,任选与式(A)中的苯环形成稠环,R’表示氢原子等)。<Image he="498" wi="700" file="DDA0002621024580000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention provides a radical polymerization initiator with excellent sensitivity and solubility in water, a composition containing the radical polymerization initiator, a cured product of the composition, a manufacturing method of the cured product and a compound. The radical polymerization initiator contains a compound represented by the general formula (A) (in the formula (A), Z 1 For direct bonding, etc., Z 2 To represent>CR 102 2 Etc. R 1 ～R 8 Represents a hydrogen atom or the like or a compound of the formula (B1) (formula (B1) wherein L 1 Represents a direct bond or the like, B represents a salt of an acidic group or the like, B represents1 to 10, representing a bonding site), R 1 ～R 8 At least one of which is a group containing a salt-forming group, R 101 Etc. represent a hydrogen atom, etc., R 1 ～R 8 1 or more hydrogen atoms in the alkyl group or the like used are optionally substituted with an ethylenically unsaturated group or the like, R 1 ～R 8 Wherein 1 or more of the methylene groups are optionally substituted with a double bond or the like, R 1 、R 2 And the adjacent groups are optionally bonded to each other to form a ring, optionally forming a condensed ring with the benzene ring in the formula (A), R' represents a hydrogen atom or the like).)

1. A radical polymerization initiator comprising a compound represented by the following general formula (A),

in the general formula (A), Z¹Is directly bonded,>NR¹⁰¹、>O、>S、>S ═ O or>C＝O；

Z²To represent>CR¹⁰² ₂、>NR¹⁰¹、>O、>S、>S ═ O or>C＝O；

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷And R⁸Each independently represents a hydrogen atom, CN, NO₂A hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms optionally substituted with an alkyl group, an aralkyl group having 7 to 30 carbon atoms optionally substituted with an alkyl group, a heterocycle-containing group having 2 to 20 carbon atoms, or a salt-forming group-containing group represented by the following general formula (B1)；

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷And R⁸At least one of which is said group comprising a salt-forming group;

R¹⁰¹and R¹⁰²Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms optionally substituted with an alkyl group, an aralkyl group having 7 to 30 carbon atoms optionally substituted with an alkyl group, or a heterocycle-containing group having 2 to 20 carbon atoms;

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷and R⁸And R¹⁰¹And R¹⁰²1 or 2 or more of the hydrogen atoms in the alkyl group, the aryl group optionally substituted with an alkyl group, the aralkyl group optionally substituted with an alkyl group, and the heterocycle-containing group used are optionally substituted with an ethylenically unsaturated group, a halogen atom, an acyl group, an acyloxy group, a substituted amino group, a sulfonamide group, a sulfonyl group, a carboxyl group, a cyano group, a sulfo group, a hydroxyl group, a nitro group, a mercapto group, an imide group, a carbamoyl group, a sulfonamide group, a phosphonic acid group, or a phosphoric acid group;

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷and R⁸And R¹⁰¹And R¹⁰²1 or 2 or more of the methylene groups in the alkyl, aryl optionally substituted with alkyl, aralkyl optionally substituted with alkyl and heterocycle-containing groups used are optionally substituted by carbon-carbon double bonds, -O-, -S-, -CO-, -O-CO-, -CO-O-, -OCO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-O-, -NR' -, -S-S-, -SO.₂-or a combination of groups selected from them under conditions where the oxygen atoms are not adjacent;

R¹and R²、R²And R³、R³And R⁴、R⁵And R⁶、R⁶And R⁷、R⁷And R⁸Optionally bonded to each other to form a ring, optionally forming a condensed ring with the benzene ring constituting the three-membered ring in the general formula (A);

r' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

in the general formula (B1), L₁A bonding group representing a direct bond or a b +1 valence;

b represents a salt of an acidic group or a salt of a basic group;

b represents an integer of 1 to 10,

denotes a site bonded to a benzene ring.

2. The radical polymerization initiator according to claim 1, wherein the compound has a maximum absorption wavelength of 380nm or more in a range of 300nm or more and 600nm or less.

3. The radical polymerization initiator according to claim 1 or 2, wherein said Z¹And said Z²In combination of>S and>and C is a combination of O.

4. The radical polymerization initiator according to any one of claims 1 to 3, wherein B is a salt of an acidic group,

said L₁Is a direct bond.

5. The radical polymerization initiator according to any one of claims 1 to 4, wherein B is a salt of an acidic group,

the anionic group constituting the salt of the acidic group is a carboxylate ionic group.

6. The radical polymerization initiator according to any one of claims 1 to 5, wherein B is a salt of an acidic group,

the cation component of the salt constituting the acidic group is an alkali metal ion, an alkaline earth metal ion, or an amine cation.

7. The radical polymerization initiator according to any one of claims 1 to 6, wherein the solubility of the compound is 0.5 parts by mass or more with respect to 100 parts by mass of water.

8. The radical polymerization initiator according to any one of claims 1 to 7, further comprising a compound represented by the following general formula (I),

in the general formula (I), X¹An aryl group having 6 to 15 carbon atoms, which is optionally substituted;

X²represents a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, a linear alkoxy group having 1 to 8 carbon atoms, a branched alkoxy group having 3 to 8 carbon atoms, or an aryl group having 6 to 15 carbon atoms optionally having a substituent;

A^m+a cationic component representing a valence of m;

m represents a number of 1 to 3;

X¹and X²Aryl radicals and X used²1 or 2 or more of the hydrogen atoms in the alkyl group or the alkoxy group to be used are optionally substituted with an ethylenically unsaturated group, a halogen atom, an acyl group, an acyloxy group, a substituted amino group, a sulfonamide group, a sulfonyl group, a carboxyl group, a cyano group, a sulfo group, a hydroxyl group, a nitro group, a mercapto group, an imide group, a carbamoyl group, a sulfonamide group, a phosphonic acid group, or a phosphoric acid group;

X¹and X²Aryl radicals and X used²1 or 2 or more methylene groups in the alkyl or alkoxy group optionally substituted by a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO-, -CO-O-, -OCO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-O-, -NR' -, -S-, -SO-, -SO₂-or a combination of groups selected from them under conditions where the oxygen atoms are not adjacent;

r' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

9. A composition comprising a compound represented by the following general formula (A) and a radically polymerizable compound,

in the general formula (A), Z¹Is directly bonded,>NR¹⁰¹、>O、>S、>S ═ O or>C＝O；

Z²To represent>CR¹⁰² ₂、>NR¹⁰¹、>O、>S、>S ═ O or>C＝O；

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷and R⁸At least one of which is the group comprising a salt-forming group,

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷and R⁸And R¹⁰¹And R¹⁰²1 or 2 or more of the hydrogen atoms in the alkyl group, the aryl group optionally substituted with an alkyl group, the aralkyl group optionally substituted with an alkyl group and the heterocycle-containing group used are optionally substituted with an ethylenically unsaturated group, a halogen atom, an acyl group, an acyloxy group, substituted ammoniaSubstituted with a group, sulfonamide, sulfonyl, carboxyl, cyano, sulfo, hydroxyl, nitro, thiol, imide, carbamoyl, sulfonamide, phosphonate, or phosphate group;

r' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

in the general formula (B1), L₁A bonding group representing a direct bond or a b +1 valence;

b represents a salt of an acidic group or a salt of a basic group;

b represents an integer of 1 to 10;

denotes a site bonded to a benzene ring.

10. The composition of claim 9, further comprising a solvent, the solvent comprising water.

11. The composition according to claim 9 or 10, further comprising a compound represented by the following general formula (I),

in the general formula (I), X¹An aryl group having 6 to 15 carbon atoms, which is optionally substituted;

A^m+a cationic component representing a valence of m;

m represents a number of 1 to 3;

r' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

12. A cured product comprising the composition according to any one of claims 9 to 11.

13. A method for producing a cured product, comprising the step of irradiating the composition according to any one of claims 9 to 11 with light.

14. A compound represented by the following general formula (A):

in the general formula (A), Z¹Is directly bonded,>NR¹⁰¹、>O、>S、>S ═ O or>C＝O；

Z²To represent>CR¹⁰² ₂、>NR¹⁰¹、>O、>S、>S ═ O or>C＝O；

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷and R⁸At least one of which is said group comprising a salt-forming group;

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷and R⁸And R¹⁰¹And R¹⁰²1 or 2 or more of the hydrogen atoms in the alkyl group, the aryl group optionally substituted with an alkyl group, the aralkyl group optionally substituted with an alkyl group and the heterocycle-containing group used are optionally substituted with an ethylenically unsaturated group, a halogen atom, an acyl group, an acyloxy group, a substituted amino group, a sulfonic acid groupAmido, sulfonyl, carboxyl, cyano, sulfo, hydroxyl, nitro, sulfydryl, imido, carbamoyl, sulfamido, phosphonic acid or phosphate group substitution;

r' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

in the general formula (B1), L₁A bonding group representing a direct bond or a b +1 valence;

b represents a salt of an acidic group or a salt of a basic group;

b represents an integer of 1 to 10;

denotes a site bonded to a benzene ring.

15. The compound of claim 14, wherein said Z¹And said Z²In combination of>S and>a combination of C ═ O,

said B is a salt of an acidic group,

the anionic group constituting the salt of the acidic group is a carboxylate ionic group,

said L₁Is a direct bond.

Technical Field

The present invention relates to a radical polymerization initiator, a composition containing the same, a cured product thereof, a method for producing the same, and a novel compound, and more particularly, to a radical polymerization initiator having excellent sensitivity and solubility in water, a composition containing the same, a cured product thereof, a method for producing the same, and a compound.

Background

Water-soluble compositions are used in various applications such as paints, inks, adhesives, and optical films. Focusing on a water-soluble initiator of a water-soluble composition, patent document 1 proposes a photopolymerization initiator having a betaine structure, patent document 2 proposes an α -aminoacetophenone having a morpholine structure, and patent document 3 proposes an acylphosphine oxide compound.

Disclosure of Invention

Problems to be solved by the invention

The initiator proposed in the above patent document has solubility in water but has the following problems: the sensitivity is low, and, for example, when a coloring material such as a pigment is blended, there are problems that curing becomes insufficient and curing becomes insufficient in a deep portion (a portion deep in the cross-sectional direction from the surface layer) of the composition.

Accordingly, an object of the present invention is to provide a radical polymerization initiator having excellent sensitivity and solubility in water, a composition containing the same, a cured product thereof, a method for producing the same, and a compound, in view of the above problems.

Means for solving the problems

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that: the present inventors have completed the present invention by finding that a compound having a predetermined three-membered ring structure and a group containing a salt-forming group can function as a radical polymerization initiator having excellent sensitivity and solubility in water.

That is, the radical polymerization initiator of the present invention is characterized by containing a compound represented by the following general formula (a).

(in the general formula (A), Z¹Is directly bonded,>NR¹⁰¹、>O、>S、>S ═ O or>C＝O；

Z²To represent>CR¹⁰² ₂、>NR¹⁰¹、>O、>S、>S ═ O or>C＝O；

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷And R⁸Each independently represents a hydrogen atom, CN, NO₂A hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms optionally substituted with an alkyl group, an aralkyl group having 7 to 30 carbon atoms optionally substituted with an alkyl group, a heterocyclic group having 2 to 20 carbon atoms or a group represented by the following general formula (B1)The group comprising a salt-forming group;

(in the general formula (B1), L₁A bonding group representing a direct bond or a b +1 valence;

b represents a salt of an acidic group or a salt of a basic group;

b represents an integer of 1 to 10;

denotes a site bonded to a benzene ring. )

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷And R⁸At least one of the foregoing groups comprising a salt-forming group;

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷and R⁸And R¹⁰¹And R¹⁰²1 or 2 or more of the methylene groups in the alkyl, aryl optionally substituted with alkyl, aralkyl optionally substituted with alkyl and heterocycle-containing groups used are optionally substituted by carbon-carbon double bonds, -O-, -S-, -CO-, -O-CO-, -CO-O-, -OCO-O-, -O-CO-O-, -S-CO-、-CO-S-、-S-CO-O-、-O-CO-S-、-CO-NH-、-NH-CO-、-NH-CO-O-、-NR’-、-S-S-、-SO₂-or a combination of groups selected from them under conditions where the oxygen atoms are not adjacent;

r' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ).

In the radical polymerization initiator of the present invention, the maximum absorption wavelength of the compound in the range of 300nm or more and 600nm or less is preferably 380nm or more. In the radical polymerization initiator of the present invention, Z is the same as Z¹And the aforementioned Z²Preferably in combination with>S and>and C is a combination of O. Further, among the radical polymerization initiators of the present invention, preferred are: b is a salt of an acidic group, L is₁Is a direct bond. Further, among the radical polymerization initiators of the present invention, preferred are: the B is a salt of an acidic group, and the anionic group constituting the salt of an acidic group is a carboxylate ionic group. Among the radical polymerization initiators of the present invention, preferred are: the B is a salt of an acidic group, and the cationic component constituting the salt of an acidic group is an alkali metal ion, an alkaline earth metal ion or an amine-based cation. In the radical polymerization initiator of the present invention, the solubility of the compound is preferably 0.5 parts by mass or more with respect to 100 parts by mass of water. The radical polymerization initiator of the present invention preferably further contains a compound represented by the following general formula (I).

(in the general formula (I), X¹An aryl group having 6 to 15 carbon atoms, which is optionally substituted;

X²represents a C1-8 linear alkyl groupA branched alkyl group having 3 to 8 carbon atoms, a linear alkoxy group having 1 to 8 carbon atoms, a branched alkoxy group having 3 to 8 carbon atoms, or an aryl group having 6 to 15 carbon atoms optionally having a substituent;

A^m+a cationic component representing a valence of m;

m represents a number of 1 to 3;

r' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. )

The composition of the present invention is characterized by containing a compound represented by the following general formula (A) and a radical polymerizable compound,

(in the general formula (A), Z¹Is directly bonded,>NR¹⁰¹、>O、>S、>S ═ O or>C＝O，

Z²To represent>CR¹⁰² ₂、>NR¹⁰¹、>O、>S、>S ═ O or>C＝O；

(in the general formula (B1), L₁A bonding group representing a direct bond or a b +1 valence;

b represents a salt of an acidic group or a salt of a basic group;

b represents an integer of 1 to 10;

denotes a site bonded to a benzene ring. )

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷And R⁸At least one of which is the aforementioned group comprising a salt-forming group,

r' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. )

The composition of the present invention preferably further comprises a solvent, and the solvent contains water. The composition of the present invention preferably further contains a compound represented by the following general formula (I).

(in the general formula (I), X¹An aryl group having 6 to 15 carbon atoms, which is optionally substituted;

A^m+a cationic component representing a valence of m;

m represents a number of 1 to 3;

X¹and X²Aryl radicals and X used²1 or 2 or more hydrogen atoms in the alkyl group or alkoxy group are optionally substituted by an ethylenically unsaturated group, a halogen atom, an acyl group, an acyloxy group,Substituted amino, sulfonamide, sulfonyl, carboxyl, cyano, sulfo, hydroxyl, nitro, sulfhydryl, imide, carbamoyl, sulfonamide, phosphonate, or phosphonate substitution;

r' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. )

The cured product of the present invention is characterized by containing the composition of the present invention.

The method for producing a cured product of the present invention is characterized by comprising a step of irradiating the composition of the present invention with light.

The compound of the present invention is characterized by being represented by the following general formula (a):

(in the general formula (A), Z¹Is directly bonded,>NR¹⁰¹、>O、>S、>S ═ O or>C＝O，

Z²To represent>CR¹⁰² ₂、>NR¹⁰¹、>O、>S、>S ═ O or>C＝O；

(in the general formula (B1), L₁A bonding group representing a direct bond or a b +1 valence;

b represents a salt of an acidic group or a salt of a basic group;

b represents an integer of 1 to 10;

denotes a site bonded to a benzene ring. )

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷And R⁸At least one of the foregoing groups comprising a salt-forming group;

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷and R⁸And R¹⁰¹And R¹⁰²1 or 2 or more of the methylene groups in the alkyl, aryl optionally substituted with alkyl, aralkyl optionally substituted with alkyl and heterocycle-containing groups used are optionally substituted by carbon-carbon double bonds, -O-, -S-, -CO-, -O-CO-, -CO-O-, -OCO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-O-, -NR' -, or,-S-S-、-SO₂-or a combination of groups selected from them under conditions where the oxygen atoms are not adjacent;

r' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. )

The compounds of the invention are preferably: z above¹And the aforementioned Z²In combination of>S and>a combination of C and O, wherein B is a salt of an acidic group, an anionic group constituting the salt of an acidic group is a carboxylate ion group, and L is₁Is a direct bond.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a radical polymerization initiator having excellent sensitivity and solubility in water, a composition containing the same, a cured product thereof, a method for producing the same, and a compound can be provided. That is, the radical polymerization initiator of the present invention has excellent sensitivity and solubility in water by containing the compound having the structure represented by the general formula (a) (hereinafter also referred to as "compound a").

Further, the maximum absorption wavelength of compound a in the range of 300nm or more and 600nm or less is 380nm or more, and thus the sensitivity is further excellent. Further, by reacting Z of Compound A with¹And Z²In combination of>S and>c ═ O in combination, so that the sensitivity and solubility in water become more excellent. Furthermore, by making B of the compound A a salt of an acidic group and L₁Is a direct bonding, so that the sensitivity becomes more excellent. Further, by making B of the compound a salt of an acidic group and making an anionic group constituting the salt of an acidic group a carboxylate ionic group, the sensitivity becomes more excellent. Further, the compound A is such that B is a salt of an acidic group and the cationic component constituting the salt of an acidic group is an alkali metal ion or an alkaline earth metalThe metal ion or the amine cation is more excellent in solubility in water. Further, the solubility of the compound a in 100 parts by mass of water is 0.5 parts by mass or more, whereby the radical polymerization initiator of the present invention is more excellent in solubility in water. Further, by including the compound represented by the general formula (I) in the radical polymerizable compound of the present invention, the sensitivity becomes more excellent.

According to the composition of the present invention, since the compound a is used, a composition having excellent sensitivity and a small content of an organic solvent can be easily obtained. By including a solvent in the composition of the present invention and including water in the solvent, excellent sensitivity can be easily obtained and the content of the organic solvent can be reduced. Further, by including the compound represented by the above general formula (I), the sensitivity becomes more excellent.

The cured product of the present invention is easily cured and generates little organic solvent.

According to the method for producing a cured product of the present invention, a cured product can be easily obtained by using the composition of the present invention, and the generation of an organic solvent is small.

The compound of the present invention can be used as a radical polymerization initiator excellent in sensitivity and solubility in water.

Among the compounds of the present invention, preferred are: z above¹And the above-mentioned Z²In combination of>S and>c ═ O, B is a salt of an acidic group, an anionic group constituting the salt of an acidic group is a carboxylate ion group, and L is₁Is a direct bond. By adopting such a structure, the compound of the present invention can be easily used as a radical polymerization initiator having more excellent sensitivity and solubility in water.

Detailed Description

The present invention relates to a radical polymerization initiator having excellent sensitivity and solubility in water, a composition containing the same, a cured product thereof, a method for producing the same, and a compound. Hereinafter, embodiments of the present invention will be described in detail.

A. Compound (I)

First, the compounds of the present invention will be described.

The compound of the present invention is represented by the following general formula (A).

Here, in the general formula (A), Z¹Is directly bonded,>NR¹⁰¹、>O、>S、>S ═ O or>C＝O，Z²To represent>CR¹⁰² ₂、>NR¹⁰¹、>O、>S、>S ═ O or>C＝O，R¹～R⁸Each independently represents a hydrogen atom, CN, NO₂A hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms optionally substituted with an alkyl group, an aralkyl group having 7 to 30 carbon atoms optionally substituted with an alkyl group, a heterocycle-containing group having 2 to 20 carbon atoms, or a group containing a salt-forming group represented by the following general formula (B1), R¹～R⁸At least one of which is a group containing a salt-forming group represented by the general formula (B1), R¹⁰¹And R¹⁰²Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms optionally substituted with an alkyl group, an aralkyl group having 7 to 30 carbon atoms optionally substituted with an alkyl group, or a heterocycle-containing group having 2 to 20 carbon atoms.

Here, in the formula (B), L₁Represents a direct bond or a B +1 valent bonding group, B represents a salt of an acidic group or a salt of a basic group, B represents an integer of 1 to 10, and x represents a site bonded to a benzene ring.

The compound a of the present invention has the above structure and can be used as a radical polymerization initiator having excellent sensitivity and solubility in water. Here, the reason why the above-mentioned structure can be used as a radical polymerization initiator having excellent sensitivity and solubility in water is presumed as follows.

That is, the compound A of the present invention has the above-mentioned general formulaThe ternary ring structure represented by formula (a) can absorb light in a wide wavelength region including long-wavelength light. For example, Z¹And Z²In combination of>S and>in the case of the combination of O, the radical polymerization initiator functions as a radical polymerization initiator capable of absorbing light in a wide wavelength region including light having a long wavelength of 360nm or more.

Further, in the compound a of the present invention, a substituent having a conjugated structure between the three-membered ring structures is used, and a component capable of absorbing light in a long wavelength region is selected as a cationic component or an anionic component which forms a salt with an anionic group or a cationic group included in the salt-forming group, so that light in a longer wavelength region can be easily absorbed than in the case of the three-membered ring structure alone.

Thus, the compound a of the present invention can absorb light in a wide wavelength range, and has excellent sensitivity. Further, by having a group containing a salt-forming group as a substituent of the three-membered ring structure, the solubility in water becomes excellent. Thus, the compound a of the present invention can be used as a radical polymerization initiator excellent in sensitivity and solubility in water.

Further, since light in a long wavelength region can be absorbed, the compound a composition of the present invention is excellent in deep-part curability, in which the composition can be stably cured even in a deep part. The compound a of the present invention is particularly useful for curing thick compositions, curing compositions containing a colorant such as a water-soluble photocurable ink, and the like, because of the deep-part curability. Further, since the compound a of the present invention has excellent solubility in water, it exhibits excellent compatibility with a water-soluble resin such as a radical polymerizable compound having a hydrophilic group such as a carboxyl group, a hydroxyl group, an acrylamide group, and an ester group, and a resin component. As a result, the compound a of the present invention can be suitably used also in, for example, a solvent-free composition by combining it with a water-soluble resin.

The compound A of the present invention is described in detail below.

1. Groups containing salt-forming groups

The compound a of the present invention has a group containing a salt-forming group represented by the above general formula (B1). Hereinafter, the salt-forming group represented by B in the general formula (B1) is referred to as "salt-forming group B".

(1) Salt-forming group B

The salt-forming group B used in the above general formula (B1) is a salt of an acidic group or a salt of a basic group. In the compound of the present invention, the salt-forming group B is preferably a salt of an acidic group. This is because: by using a salt in which the salt-forming group B is an acidic group, the compound a of the present invention can be used as a radical polymerization initiator having more excellent sensitivity. Here, the salt of an acidic group comprises a bond to L₁And a cationic component forming a salt with the anionic group. In addition, salts of basic groups comprise a linkage to L₁And an anionic component forming a salt with the cationic group. Furthermore, the anion and cation contained in the salt-forming group B may have the same valence. For example, when the salt-forming group B is a salt of an acidic group, in the case where the anionic group is a 2-valent anion, 2 cation components having a valence of 1 may be contained, and 1 cation component having a valence of 2 may be contained.

(1-1) salts of acidic groups

As the anionic group constituting the salt of the acid group, any anionic group may be used as long as it can impart desired sensitivity and solubility in water to the compound a, and a phosphate ion group, a carboxylate ion group, a sulfonate ion group, a phosphate ion group, a sulfate ion group, a nitrate ion group, a phosphite ion group, a phosphonate ion group, a phosphinate ion group, a sulfinate ion group, or the like may be used. Among them, preferred is a carboxylate ion group (-COO)^-) Sulfonate ion group (-SO)₃ ^-) Particularly preferred is a carboxylate ion group (-COO)^-). This is because: the compound A of the present invention is useful as a radical polymerization initiator having more excellent sensitivity.

The cationic component that forms a salt with the anionic group may be any cationic component that can impart desired sensitivity and solubility in water to the compound a. These cationic components may be inorganic ions or organic ions.

Examples of the inorganic ions include alkali metal ions and alkaline earth metal ions.

Examples of the organic ion include a tertiary sulfonium cation, a tertiary oxonium cation, a quaternary phosphonium cation, an amine cation, and a tertiary carbocation.

In the compound a of the present invention, the cation component is preferably an alkali metal ion, an alkaline earth metal ion, or an amine cation from the viewpoint of easy synthesis, and among them, an alkali metal ion or an amine cation is preferred. This is because: by using the cation component as the ion, the solubility of compound a in water and the storage stability become more excellent.

Examples of the alkali metal ion include lithium ion, sodium ion, potassium ion, rubidium, and cesium. Among them, potassium ion is preferable. This is because: the compound A of the present invention is useful as a radical polymerization initiator having more excellent solubility in water.

Examples of the alkaline earth metal ion include magnesium ion and calcium ion.

As the amine cation, any cation may be used as long as the nitrogen atom has a positive charge, and ammonium cation (N)⁺H₄) Primary to quaternary ammonium cations can be used. Among them, tertiary ammonium cations and quaternary ammonium cations are preferable, and tertiary ammonium cations are particularly preferable. This is because: when the amine cation is the cation, the solubility of the compound a of the present invention in water is further improved.

As the tertiary ammonium cation, for example, a cation represented by the following general formula (C3) (hereinafter also referred to as cation C3) can be used. When a plurality of ammonium cations are contained in 1 molecule, the ammonium cation can be regarded as an ammonium cation having the largest number of substitutions. For example, a cation comprising a tertiary ammonium cation within 1 molecule and at least one of a secondary ammonium cation and a primary ammonium cation can be considered to correspond to a tertiary ammonium cation.

N⁺HY¹Y²Y³(C3)

Here, in the general formula (C3), Y¹、Y²And Y³Each independently represents a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms or an aralkyl group having 7 to 13 carbon atoms.

Y¹、Y²And Y³The hydrogen atoms in the radicals being optionally substituted by hydroxy groups, Y¹、Y²And Y³Methylene groups in the radicals indicated being optionally bound by oxygen atoms or-N⁺H-substituted, Y¹、Y²And Y³Any two or more of them are optionally bonded to form a ring.

As the above Y¹～Y³Examples of the alkyl group having 1 to 6 carbon atoms to be used include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a tert-pentyl group, and a hexyl group.

As the above Y¹～Y³Examples of the alkenyl group having 2 to 6 carbon atoms to be used include vinyl, ethylene, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, and 5-hexenyl.

As the above Y¹～Y³Examples of the aryl group having 6 to 15 carbon atoms to be used include a phenyl group, a trimethylphenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group and the like.

As the above Y¹～Y³The aralkyl group having 7 to 13 carbon atoms used means a group having 7 to 13 carbon atoms in which a hydrogen atom of an alkyl group is substituted with an aryl group, and examples thereof include a benzyl group, α -methylbenzyl group, α -dimethylbenzyl group, phenylethyl group, naphthylpropyl group and the like.

In the compound A of the present invention, the above-mentioned Y is preferred¹～Y³2 or more of them are bonded to form a ring. This is because: the solubility and sensitivity of the compound a of the present invention in water become more excellent. The following compounds Nos. A1 to A14 show Y as a cation C3¹～Y³Wherein 2 or more of the above groups are bonded to form a ring.

In the compound A of the present invention, Y is as defined above¹～Y³The hydrogen atom(s) of (a) is preferably substituted by more than one hydroxyl group. This is because: the solubility of the compound a of the present invention in water becomes more excellent. The compounds Nos. A5 to A6 and A15 to A34 described later represent Y in the cation C3¹～Y³Examples of the hydrogen atom(s) of (2) are substituted with one or more hydroxyl groups.

More specifically, the cation C3 includes the following compound Nos. A1 to A34.

As the quaternary ammonium cation, for example, a cation represented by the following general formula (C4) can be used.

N⁺Y¹Y²Y³Y⁴(C4)

Here, in the general formula (C4), Y¹、Y²、Y³And Y⁴Each independently represents a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms or an aralkyl group having 7 to 13 carbon atoms.

For the above Y¹、Y²、Y³And Y⁴The alkyl group having 1 to 6 carbon atoms, alkenyl group having 2 to 6 carbon atoms, aryl group having 6 to 15 carbon atoms or aralkyl group having 7 to 13 carbon atoms used may be the same as Y in the general formula (C3)¹Etc. the groups used are the same.

More specifically, the quaternary ammonium cation includes tetraalkylammonium, pyrrolidine cation, imidazolium cation, piperidinium cation, imidazoline cation, morpholinium cation, and piperazinium cation.

Examples of the tetraalkylammonium include tetramethylammonium, ethyltrimethylammonium, diethyldimethylammonium, triethylmethylammonium, and tetraethylammonium.

Examples of the pyrrolidine cation include N, N-dimethylpyrrolidinium, N-ethyl-N-methylpyrrolidinium, N-diethylpyrrolidinium, spiro- (1,1 ') -bipyrrolidinium, and piperidine-1-spiro-1' -pyrrolidinium.

Examples of the imidazolium cation include N, N ' -dimethylimidazolium, N-ethyl-N ' -methylimidazolium, N ' -diethylimidazolium, 1-ethyl-2, 3-dimethylimidazolium, 1,2, 3-trimethylimidazolium, and 1,2,3, 4-tetramethylimidazolium.

Examples of the piperidinium cation include pyridinium cations such as N-methylpyridinium, N-ethylpyridinium and 1, 2-dimethylpyridinium; n, N-dimethylpiperidinium, N-ethyl-N-methylpiperidinium, N-diethylpiperidinium and the like.

Examples of the imidazoline cation include N, N-dimethylimidazoline, N-ethyl-N '-methylimidazoline, N-diethylimidazoline, 1,2,3, 4-tetramethylimidazoline, 1,3, 4-trimethyl-2-ethylimidazoline, 1, 3-dimethyl-2, 4-diethylimidazoline, 1, 2-dimethyl-3, 4-diethylimidazoline, 1-methyl-2, 3, 4-triethylimidazoline, 1,2,3, 4-tetraethylimidazoline, 1,2, 3-trimethylimidazoline, 1, 3-dimethyl-2-ethylimidazoline, 1-ethyl-2, 3-dimethylimidazoline, 1-ethyl-2-methylimidazolium, N-ethyl-N' -methylimidazolium, N-diethylimidazoline, 1,2,3, 4-tetramethylimidazoline, 1,2,3, 4-tetraethylimidazoline, 1,2, 3-trimethyl, 1,2, 3-triethylimidazoline, and the like.

Examples of the morpholinium cation include N, N-dimethylmorpholinium, N-ethyl-N-methylmorpholinium, and N, N-diethylmorpholinium.

Examples of the piperazinium cation include piperazinium cations such as N, N ' -tetramethylpiperazinium, N-ethyl-N, N ' -trimethylpiperazinium, N-diethyl-N ', N ' -dimethylpiperazinium, N ' -triethyl-N ' -methylpiperazinium, and N, N ' -tetraethylpiperazinium.

As the primary ammonium cation and the secondary ammonium cation, for example, cations represented by the following general formula (C1) and general formula (C2), respectively, can be used.

N⁺H₂Y¹Y²(C2)

N⁺H₃Y¹(C1)

Here, Y in the general formula (C2)¹And Y²And Y in the formula (C1)¹Each independently represents a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms or an aralkyl group having 7 to 13 carbon atoms.

For the above Y¹And Y²The alkyl group having 1 to 6 carbon atoms, alkenyl group having 2 to 6 carbon atoms, aryl group having 6 to 15 carbon atoms or aralkyl group having 7 to 13 carbon atoms used may be the same as Y in the general formula (C3)¹Etc. the groups used are the same.

More specifically, the primary ammonium cation includes cations such as octylamine, dodecylamine, laurylamine, tetradecylamine, hexadecylamine, stearylamine, oleylamine, allylamine, benzylamine, and aniline. The cation of aniline specifically represents C₆H₅-N⁺H³Cations are shown.

More specifically, the secondary ammonium cation includes cations such as dilaurylamine, ditetradecylamine, dihexadecylamine, distearylamine, and N-methylaniline. Further, as the secondary ammonium cation, the following compounds No. a51 to No. a57 and the like can be used.

Examples of the tertiary sulfonium cation include (2-carboxyethyl) dimethylsulfonium, (3-chloropropyl) diphenylsulfonium, cyclopropyldiphenylsulfonium, diphenyl (methyl) sulfonium, tri-n-butylsulfonium, tri-p-tolylsulfonium, triethylsulfonium, trimethylsulfonium, and triphenylsulfonium.

Examples of the tertiary oxonium cation include triethyloxonium and trimethyloxonium.

Examples of the quaternary phosphonium cation include tetrabutylphosphonium and butyltriphenylphosphonium.

Examples of the tertiary carbocation include trisubstituted carbocations such as a triphenyl carbocation and a tri (substituted phenyl) carbocation. Examples of the tri (substituted phenyl) carbocation include a tri (methylphenyl) carbocation, a tri (dimethylphenyl) carbocation and the like.

As the above-mentioned cationic component, a compound represented by the following general formula (a2) (hereinafter, may be referred to as "compound a 2") can be preferably used from the viewpoint of improving the absorption efficiency of light in a long wavelength region, etc., and making it easier to adjust the absorption wavelength. That is, the compound a of the present invention may be a compound in which a salt of a compound having an acidic group and a salt of a compound having a basic group B form a salt among the compounds a represented by the above general formula (a), in other words, a compound in which an anionic group included in a salt-forming group of one compound a forms a salt with a cationic group included in a salt-forming group of another compound a.

In the general formula (A2), Z¹¹Is directly bonded,>NR²⁰¹、>O、>S、>S ═ O or>C＝O，Z¹²To represent>CR²⁰² ₂、>NR²⁰¹、>O、>S、>S ═ O or>C＝O，R¹¹～R¹⁸Each independently represents a hydrogen atom, CN, NO₂A hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms or a group containing a cationic group represented by the following general formula (B2), R¹¹～R¹⁸At least 1 of the above groups being a group containing the above cationic group, R²⁰¹And R²⁰²Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocycle-containing group having 2 to 20 carbon atoms.

In the general formula (B2), L₁₁Represents a direct bond or a B2+1 valent bonding group, B2 represents a cationic group, B2 represents an integer of 1 to 10, and represents a site bonded to a benzene ring.

L used for the general formula (B2)₁₁And b2, L may be L described in the section "(2) other section" mentioned later₁Among them, the salt-forming group B is preferably a salt of a basic group, as in B. The cationic group represented by the general formula (B2) may be the same as the cationic group described in the section "(1-2) salt of basic group" described later. This is because: by adopting such a structure, the compound a of the present invention is excellent in dispersion stability and ease of synthesis.

Z used for the general formula (A2)¹¹And Z¹²、R¹¹～R¹⁸And R²⁰¹And R²⁰²Z may be the same as Z described in "2. Compound A" mentioned later¹And Z²、R¹～R⁸And R¹⁰¹And R¹⁰²The same is true.

Examples of the compound a containing the compound a2 as a cationic component include the following general formulae (53) to (60). Further, as the compound a2, a compound obtained by combining sites containing a cationic group in a compound having a salt containing a basic group described in general formulae (29) to (52) described later as the salt-forming group B may be used.

(1-2) salts of basic groups

The cationic group constituting the salt of the basic group may be any cationic group having a valence of 1 or more, and examples thereof include a tertiary sulfonium cationic group, a tertiary oxonium cationic group, a quaternary phosphonium cationic group, a quaternary ammonium cationic group, and a tertiary carbocation. Among them, quaternary ammonium cationic groups are preferable. This is because: when the cationic group is the group, a salt having good storage stability can be formed between the cationic component and the anionic group.

The tertiary sulfonium cation group may be a group represented by the following general formula (C11), specifically, a structure in which a substituent bonded to the S atom of the compounds listed as the tertiary sulfonium cation is removed.

The tertiary oxonium cation group may be a group represented by the following general formula (C12), specifically, a group obtained by removing one substituent bonded to an O atom of the compounds listed as the tertiary oxonium cation.

The quaternary phosphonium cation group may be a group represented by the following general formula (C13), specifically, a group obtained by removing a substituent bonded to a P atom of a compound exemplified as the quaternary phosphonium cation.

The quaternary ammonium cation group may be a group represented by the following general formula (C14), specifically, a group obtained by removing one substituent bonded to the N atom of the compound exemplified as the quaternary ammonium cation.

The tertiary carbocation group may be a group represented by the following general formula (C15), specifically, a group obtained by removing one substituent bonded to a C atom of a compound exemplified as the tertiary carbocation.

In the general formulae (C11) to (C15), R⁴⁰¹Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocycle-containing group having 2 to 20 carbon atoms, and in the general formula (C14), 2 or 3R' s⁴⁰¹Optionally forming a ring. In general formulae (C11) to (C15), and L₁₁The site of bonding.

For R⁴⁰¹The alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 30 carbon atoms, the aralkyl group having 7 to 30 carbon atoms and the heterocycle-containing group having 2 to 20 carbon atoms to be used may be the same asR described in the section "2. Compound A" mentioned later¹And the like in the groups used.

As 2R in the formula (C14)⁴⁰¹Examples of the group having a ring formed thereon include a pyrrolidinium cationic group, a morpholinium cationic group, and a piperazinium cationic group. As 3R in the formula (C14)⁴⁰¹Examples of the group forming a ring include a pyridinium cation group and the like.

The anionic component forming a salt with the cationic group may be any component as long as the compound a can exhibit water solubility. Examples of the anion component include halogen anions such as chloride anion, bromide anion, iodide anion, and fluoride anion; inorganic system anions such as perchlorate anion, chlorate anion, thiocyanate anion, hexafluorophosphate anion, antimony hexafluoride anion, arsenic hexafluoride anion, boron tetrafluoride anion and the like; methanesulfonate ion, fluorosulfonate ion, benzenesulfonate anion, toluenesulfonate anion, 1-naphthylsulfonate anion, 2-naphthylsulfonate anion, trifluoromethanesulfonate anion, pentafluoroethanesulfonate anion, heptafluoropropanesulfonate anion, nonafluorobutanesulfonate anion, undecafluoropentanesulfonate anion, tridecafluorohexanesulfonate anion, pentadecafluoroheptadecafluorooctanesulfonate anion, heptadecafluorooctanesulfonate anion, perfluoro-4-ethylcyclohexanesulfonate ion, N-alkyl (or aryl) diphenylamine-4-sulfonate anion, 2-amino-4-methyl-5-chlorobenzenesulfonate anion, 2-amino-5-nitrobenzenesulfonate anion, sulfonate anion described in Japanese patent laid-open publication No. 2004-53799, Organic sulfonate anions such as camphorsulfonate anion, fluorobenzenesulfonate anion, difluorobenzenesulfonate anion, trifluorobenzenesulfonate anion, tetrafluorobenzenesulfonate anion, pentafluorobenzenesulfonate anion, and the like; organic phosphoric acid-based anions such as octyl phosphate anion, dodecyl phosphate anion, octadecyl phosphate anion, phenyl phosphate anion, nonylphenyl phosphate anion, and 2, 2' -methylenebis (4, 6-di-t-butylphenyl) phosphonate anion; organic fluorosulfonyl imide ions such as bis (trifluoromethane) sulfonyl imide ion, bis (pentafluoroethane) sulfonyl imide ion, bis (heptafluoropropane) sulfonyl imide ion, bis (nonafluorobutane) sulfonyl imide ion, bis (undecafluoropentane) sulfonyl imide ion, bis (pentadecafluoroheptane) sulfonyl imide ion, bis (tridecafluorohexane) sulfonyl imide ion, bis (heptadecafluorooctane sulfonyl imide) ion, (trifluoromethane) (nonafluorobutane) sulfonyl imide ion, (methane) (trifluoromethane) sulfonyl imide ion, and cyclohexafluoropropane-1, 3-bis (sulfonyl) imide anion; tetrakis (pentafluorophenyl) borate anion, tetrakis (4-fluorophenyl) borate ion, tetraphenylborate ion, borate anion described in Japanese patent application laid-open No. 2008-81470, borate anion described in Japanese patent application laid-open No. 2007-112854, borate anion described in Japanese patent application laid-open No. 6-184170, borate anion described in Japanese patent application laid-open No. 2002-526391, tetraarylborate anion such as borate anion described in International application laid-open No. PCT/JP2008/069562, various aliphatic or aromatic carboxylate anions, tris (trifluoromethanesulfonyl) methide, tris (methylsulfonyl) methide and other organic sulfonyl methide ions, and furthermore, alkylsulfonate ion, fluorine-substituted alkylsulfonate ion, alkylsulfonamide, and the like are exemplified, Fluorine-substituted alkylsulfonylimides are substituted with acryloyloxy group, methacryloyloxy group, or aliphatic cyclic alkyl groups such as norbornyl group and adamantyl group. Further, a quencher anion having a function of deactivating (quenching) the active molecule in an excited state; anions of metallocene compounds such as ferrocene and ruthenocene having an anionic group such as a carboxyl group, a phosphonic acid group or a sulfonic acid group in the cyclopentadiene ring.

Among the above anion components, a halogen anion is preferable, and a chloride anion, a bromide anion and the like are particularly preferable. This is because: by making the anion component the ion, the ease of synthesis, storage stability, and the like of the compound a become excellent.

(2) Others

B in the general formula (B1) represents an integer of 1 to 10, and L₁Salts of bonded acidic groups orThe number of salts of the basic group, i.e. the number of salt groups B. In the compound a of the present invention, b is preferably an integer of 1 to 5, more preferably an integer of 1 to 2, and particularly preferably 1, as long as it can impart a desired sensitivity and solubility in water to the compound a. This is because: when the amount of b is in the above range, the dispersion stability and the ease of synthesis of the compound a are excellent.

L used in the above general formula (B1)₁Represents a direct bond or a b +1 valent bonding group. L used as a bonding group having a valence of b +1₁Can represent a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a group represented by the following (II-a) or (II-b),>C＝O、-NH-CO-、-CO-NH-、>NR⁵³Or an aliphatic hydrocarbon group having 1 to 120 carbon atoms and having a valence equal to b +1, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic ring-containing group having 2 to 35 carbon atoms.

R is as defined above⁵³The aromatic hydrocarbon compound may be a hydrocarbon group containing a hydrogen atom, an aliphatic hydrocarbon group having 1 to 120 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic ring-containing group having 2 to 35 carbon atoms.

As L₁And R⁵³The methylene group in the aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group and heterocyclic ring-containing group used is sometimes represented by-O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-O-, -NR' -, -S-, -SO₂A nitrogen atom or a combination thereof, a hydrogen atom of the methylene group being optionally substituted by a hydroxyl group, and the above aromatic ring or heterocyclic ring being sometimes fused with other rings. Wherein the bonding group L₁When it is a nitrogen atom, a phosphorus atom or a bonding group represented by the following (II-a) or (II-b), b +1 is 3, and the bonding group L₁Is an oxygen atom or a sulfur atom,>C ═ O, -NH-CO-, -CO-NH-, or>NR⁵³When b +1 is 2.

As R⁵³Examples of the aliphatic hydrocarbon group having 1 to 120 carbon atoms to be used include alkyl groups such as methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, isopentyl, tert-pentyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, bicyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tert-heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl and decyl; alkoxy groups such as a methyloxy group, an ethyloxy group, a propyloxy group, an isopropyloxy group, a butyloxy group, a sec-butyloxy group, a tert-butyloxy group, an isobutyloxy group, a pentyloxy group, an isopentyloxy group, a tert-pentyloxy group, a hexyloxy group, a cyclohexyloxy group, a heptyloxy group, an isoheptyloxy group, a tert-heptyloxy group, an n-octyloxy group, an isooctyloxy group, a tert-octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, and a decyloxy group; alkylthio groups such as methylthio, ethylthio, propylthio, isopropylthio, butylthio, sec-butylthio, tert-butylthio, isobutylthio, pentylthio, isopentylthio, tert-pentylthio, hexylthio, cyclohexylthio, heptylthio, isoheptylthio, tert-heptylthio, n-octylthio, isooctylthio, tert-octylthio, and 2-ethylhexylthio; alkenyl groups such as vinyl, 1-methylvinyl, 2-propenyl, 1-methyl-3-propenyl, 3-butenyl, 1-methyl-3-butenyl, isobutenyl, 3-pentenyl, 4-hexenyl, cyclohexenyl, bicyclohexenyl, heptenyl, octenyl, decenyl, pentadecenyl, eicosenyl and tricosenyl, and groups obtained by substituting these groups with substituents described later.

As R⁵³Examples of the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms include aralkyl groups such as benzyl, phenethyl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl and the like; aryl groups such as phenyl and naphthyl; aryloxy groups such as phenoxy and naphthoxy; arylthio groups such as phenylthio and naphthylthio, and groups obtained by substituting these groups with substituents described later.

As R⁵³The heterocyclic group having 2 to 35 carbon atoms is usedExamples of the substituent include pyridyl, pyrimidyl, pyridazinyl, piperidyl, pyranyl, pyrazolyl, triazinyl, pyrrolyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, pyranyl, benzofuryl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 2-pyrrolidin-1-yl, 2-piperidone-1-yl, 2, 4-dioxoimidazolidin-3-yl, 2, 4-dioxooxazolidin-3-yl, benzotriazolyl, and the like, and those groups in which these groups are substituted with the substituents described later.

The above-mentioned bonding group L₁The structure of the aliphatic hydrocarbon group having 1 to 120 carbon atoms and having a valence equal to b +1 to be used can be appropriately set according to the use of the compound A of the present invention and the like. The aliphatic hydrocarbon group may be any of a linear, branched, cyclic (alicyclic hydrocarbon), and a combination thereof.

Furthermore, the methylene group in the above aliphatic hydrocarbon group is optionally substituted by-O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-O-, -NR' -, -S-, -SO-, -₂Or a nitrogen atom or a combination thereof.

As the above-mentioned bonding group L₁The aliphatic hydrocarbon group having 1 to 120 carbon atoms and having a valence of 2 or more used may be represented by R⁵³The aliphatic hydrocarbon group having 1-120 carbon atoms is one in which a part of hydrogen atoms are removed.

As the above-mentioned bonding group L₁The aliphatic hydrocarbon group having 1 to 120 carbon atoms and having a valence of 2 used includes, specifically, an alkylene group such as a methylene group, an ethylene group, a propylene group, a butylene group, or a butylene group; a group obtained by substituting methylene of the above alkylene group with-O-, -S-, -CO-O-, -O-CO-; residues of diols such as ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, and hexylene glycol; residues of dithiols such as ethanedithiol, propanedithiol, butanedithiol, pentanethiol and hexanedithiol, and those substituted with substituents described later, and the like.

As mentioned aboveA bonding group L₁The b +1 used is an aliphatic hydrocarbon group having 1 to 120 carbon atoms and having a valence of 3, and specific examples thereof include an alkylidene group such as a propylidene group or a1, 1, 3-butylidene group, and a group obtained by substituting these groups with a substituent described later.

The above-mentioned bonding group L₁The structure of the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and a valence equal to b +1 to be used can be appropriately set according to the use of the compound A of the present invention.

Furthermore, methylene in the aromatic ring-containing hydrocarbon group is optionally replaced with-O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-O-, -NR' -, -S-, -SO-, -SO₂Or a nitrogen atom or a combination thereof.

As the above-mentioned bonding group L₁The aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and having a valence of 2 or more used may be represented by R⁵³The aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and a valence of 1 is one wherein some hydrogen atoms are removed.

As the above-mentioned bonding group L₁The 2-valent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms to be used includes, specifically, arylene groups such as phenylene and naphthylene; residues of bifunctional phenols such as catechol and bisphenol; 2,4,8, 10-tetraoxaspiro [5, 5]]Undecane, and the like, and those obtained by substituting these groups with substituents described later.

As the above-mentioned bonding group L₁Examples of the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and a valence of 3 used include phenyl-1, 3, 5-trimethylene group and those obtained by substituting these groups with a substituent described later.

The above-mentioned bonding group L₁The structure of the heterocycle-containing group having 2 to 35 carbon atoms and having a valence equal to b +1 to be used may be appropriately set according to the use of the compound A of the present invention.

Furthermore, the methylene group in the above-mentioned heterocycle-containing group is optionally substituted by-O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-、-NH-CO-O-、-NR’-、-S-S-、-SO₂Or a nitrogen atom or a combination thereof.

As the above-mentioned bonding group L₁The heterocyclic group having 2 to 35 carbon atoms and having a valence of 2 or more used may be, for example, one selected from the group consisting of R⁵³The heterocyclic group having 2 to 35 carbon atoms and having 1-valent carbon atoms is one in which some hydrogen atoms are removed.

As the above-mentioned bonding group L₁Specific examples of the heterocyclic group having 2-35 carbon atoms and having a valence of 2 used include a pyridine ring, a pyrimidine ring, a piperidine ring, a piperazine ring, a triazine ring, a furan ring, a thiophene ring, an indole ring, and the like, and a group obtained by substituting these groups with a substituent described later.

As the above-mentioned bonding group L₁Examples of the heterocyclic group having 2 to 35 carbon atoms and having a valence of 3 to be used include a group having an isocyanuric ring, a group having a triazine ring, and a group obtained by substituting these groups with a substituent described later.

The functional groups such as the aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group, and heterocyclic ring-containing group may optionally have a substituent, and are unsubstituted or substituted unless otherwise specified. As the substituent for substituting a hydrogen atom such as such an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group and a heterocyclic ring-containing group, there may be mentioned a substituent for substituting R described in the section "2. Compound A" mentioned later¹The same applies to the substituents of hydrogen atoms such as alkyl groups used. As the substituent, for example, a hydrophilic group such as a hydroxyl group can be used from the viewpoint of further improving the solubility of compound a in water.

When the salt-forming group B is a salt of an acidic group, the above-mentioned bonding group L₁Preferably directly bonded,>C＝O、-NH-CO-、-CO-NH-、>NR⁵³Or an aliphatic hydrocarbon group having 1 to 120 carbon atoms and having a valence equal to b +1, wherein the aliphatic hydrocarbon group is preferably directly bonded or an aliphatic hydrocarbon group having 1 to 20 carbon atoms and having a valence equal to b +1, and particularly preferably directly bonded, that is, a salt of an acidic group is directly bonded to a benzene ring. This is because: the compound A of the present invention is useful as a radical polymerization initiator having more excellent sensitivity. This is because: for example, when the anionic group constituting the salt-forming group B is a carboxylate ion group or the like, a conjugated structure is easily formed between the three-membered ring structure and the group including the salt-forming group B, and as a result, light in a long wavelength region is more easily absorbed than when the three-membered ring structure is present alone.

When the salt-forming group B is a salt of a basic group, the above-mentioned bonding group L₁The aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms, and particularly preferably has 2 to 10 carbon atoms. This is because: the compound a is excellent in dispersion stability and ease of synthesis.

When the salt-forming group B is a salt of a basic group, the above-mentioned bonding group L₁Wherein methylene groups of the above aliphatic hydrocarbon groups, aromatic ring-containing hydrocarbon groups and heterocyclic ring-containing groups are optionally substituted by-O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-O-, -NR' -, -S-, -SO₂Or a combination thereof, wherein the end on the benzene ring side is preferably substituted by-O-, particularly preferably substituted by-O-, i.e., L₁The terminal of (a) is bonded to the benzene ring via-O-. This is because: by adopting the above structure, the compound a of the present invention is excellent in the ease of synthesis.

In the compound A of the present invention, R¹～R⁸At least one of which is a group comprising a salt-forming group B. The number of groups comprising a salt-forming group B, i.e. as R¹～R⁸The amount of (b) is not more than 8, preferably not less than 1 and not more than 2, and preferably 1, in the compound a, as long as the compound a can be provided with desired sensitivity and solubility in water. This is because: when the amount is within the above range, the compound a of the present invention is excellent in the ease of synthesis, storage stability, solubility in water, and the like.

The bonding position of the group containing the salt-forming group B may be R as long as it can impart desired sensitivity and solubility in water to the compound a¹～R⁸Contains, for example, preferably R⁴. This is because: by adopting such a structure, the compound a of the present invention is excellent in the ease of synthesis and the like. Furthermore, this is because: the compound a of the present invention is excellent in storage stability, solubility in water, and the like.

2. Compound A

As R¹～R⁸And R¹⁰¹And R¹⁰²Examples of the alkyl group having 1 to 20 carbon atoms to be used include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a pentyl group, an isopentyl group, a tert-pentyl group, a cyclopentyl group, a hexyl group, a 2-hexyl group, a 3-hexyl group, a cyclohexyl group, a 4-methylcyclohexyl group, a heptyl group, a 2-heptyl group, a 3-heptyl group, an isoheptyl group, a tert-heptyl group, a 1-octyl group, an isooctyl group, a tert-octyl.

As R¹～R⁸And R¹⁰¹And R¹⁰²Examples of the aryl group having 6 to 30 carbon atoms to be used include a phenyl group, a naphthyl group, and an anthryl group.

Further, 1 or 2 or more hydrogen atoms in the above aryl group are optionally substituted with an alkyl group. As the alkyl group substituting for a hydrogen atom in the aryl group, the above-mentioned R may be used¹And the alkyl group having a predetermined carbon number among the alkyl groups having 6 to 20 carbon atoms used.

As R¹～R⁸And R¹⁰¹And R¹⁰²Examples of the aralkyl group having 1 to 20 carbon atoms and 7 to 30 carbon atoms to be used include benzyl, fluorenyl, indenyl, and 9-fluorenylmethyl groups.

Further, 1 or 2 or more hydrogen atoms in the above aralkyl group are optionally substituted with an alkyl group. As the alkyl group substituting for the hydrogen atom in the aralkyl group, the above-mentioned R may be used¹And the alkyl group having a predetermined carbon number among the alkyl groups having 6 to 20 carbon atoms used.

As R¹～R⁸And R¹⁰¹And R¹⁰²Examples of the heterocyclic group having 2 to 20 carbon atoms to be used include pyridyl, pyrimidyl, pyridazinyl, piperidyl, pyranyl, pyrazolyl and triazinylPyrrolyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, benzofuryl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 2-pyrrolidin-1-yl, 2-piperidone-1-yl, 2, 4-dioxoimidazolidin-3-yl, 2, 4-dioxooxazolidin-3-yl and the like.

The above-mentioned functional groups such as an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, and a heterocycle-containing group having 2 to 20 carbon atoms are unsubstituted or substituted unless otherwise specified.

In the compound of the present invention, when a hydrogen atom in a group is substituted with a substituent, the number of carbon atoms in the group means the number of carbon atoms in the group after the substitution. For example, when a hydrogen atom of the alkyl group having 1 to 20 carbon atoms is substituted, the carbon number of 1 to 20 refers to the carbon number after the hydrogen atom is substituted, and does not refer to the carbon number before the hydrogen atom is substituted. In the compound of the present invention, the case where a methylene group in a group having a predetermined number of carbon atoms is substituted with a divalent group means the number of carbon atoms of the group before the substitution. For example, in the present specification, the number of carbon atoms of a group in which a methylene group in an alkyl group having 1 to 20 carbon atoms is substituted with a divalent group is 1 to 20.

Examples of the substituent for substituting a hydrogen atom of such an alkyl group, aryl group, aralkyl group, heterocyclic group, etc. include ethylenically unsaturated groups such as vinyl group, allyl group, acryloyl group, methacryloyl group, etc.; halogen atoms such as fluorine, chlorine, bromine and iodine; acyl groups such as acetyl, 2-chloroacetyl, propionyl, octanoyl, acryloyl, methacryloyl, phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyl, oxalyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl, and carbamoyl; acyloxy groups such as acetoxy and benzoyloxy; amino, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, chlorophenylamino, toluidino, methoxyanilino, N-methylanilino, diphenylamino, naphthylamino, 2-pyridylamino, methoxycarbonylamino, phenoxycarbonylamino, acetylamino, benzoylamino, formylamino, pivaloylamino, lauroylamino, carbamoylamino, N-dimethylaminocarbonylamino, N-diethylaminocarbonylamino, morpholinocarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, N-octadecyloxycarbonylamino, N-methylmethoxycarbonylamino, phenoxycarbonylamino, sulfamoylamino, cyclopentylamino, cyclopentyloxycarbonylamino, N-methylphenoxycarbonylamino, N-ethylhexylamino, 2-pyridyloxycarbonylamino, N-octylcarbonylamino, N-ethylhexylamino, N-ethylhexyl, Substituted amino groups such as N, N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino and the like; sulfonamide, sulfonyl, carboxyl, cyano, sulfo, hydroxyl, nitro, sulfhydryl, imide, carbamoyl, sulfonamide, phosphonate, phosphate, and the like.

Namely, R¹、R²、R³、R⁴、R⁵、R⁶、R⁷And R⁸And R¹⁰¹And R¹⁰²1 or 2 or more of the hydrogen atoms in the alkyl group, aryl group, aralkyl group and heterocycle-containing group used are optionally substituted with an ethylenically unsaturated group, a halogen atom, an acyl group, an acyloxy group, a substituted amino group, a sulfonamide group, a sulfonyl group, a carboxyl group, a cyano group, a sulfo group, a hydroxyl group, a nitro group, a mercapto group, an imide group, a carbamoyl group, a sulfonamide group, a phosphonic acid group or a phosphoric acid group.

The methylene group in the alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 30 carbon atoms, the aralkyl group having 7 to 30 carbon atoms, and the heterocycle-containing group having 2 to 20 carbon atoms is selected from the group consisting of a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-O-, -NR' -, -S-S-or-SO.₂The group represented by (a) is a group obtained by substituting 1 or more of the groups combined under the condition that oxygen atoms are not adjacent to each other or an unsubstituted group. R' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

Namely, R¹、R²、R³、R⁴、R⁵、R⁶、R⁷And R⁸And R¹⁰¹And R¹⁰²1 or 2 or more of methylene groups in the alkyl, aryl, aralkyl and heterocycle-containing groups used are optionally substituted by a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO-, -CO-O-, -OCO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-O-, -NR '-, -S-, -SO-O-, -CO-O-, -NH-CO-O-, -NR' -, -S-, -SO₂Or a combination of groups selected from them under conditions where the oxygen atoms are not adjacent. R' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

The group substituted with a divalent group such as-O-may be a group substituted with a terminal methylene group, and may include, for example, an alkoxy group in which a terminal methylene group in an alkyl group is substituted with-O-.

Furthermore, R¹、R²、R³、R⁴、R⁵、R⁶、R⁷And R⁸And R¹⁰¹And R¹⁰²The alkyl group, aryl group, aralkyl group and heterocycle-containing group to be used are optionally substituted with 1 or 2 or more of hydrogen atoms in the group by a substituent, and 1 or 2 or more of methylene groups in the group by the above-mentioned divalent group.

For example, as exemplified in the following formulae (302) and (303), etc., R is¹、R²、R³、R⁴、R⁵、R⁶、R⁷And R⁸And R¹⁰¹And R¹⁰²Also, a group in which 1 or 2 or more methylene groups in an alkyl group are substituted with-O-, and 1 or 2 or more hydrogen atoms in the alkyl group are substituted with a hydroxyl group may be used.

With respect to R¹～R⁸，R¹And R²、R²And R³、R³And R⁴、R⁵And R⁶、R⁶And R⁷、R⁷And R⁸Are optionally bonded to each other to form a ring, and further, optionally with a compound of formula(A) The benzene rings constituting the three-membered ring in (1) form a condensed ring.

Examples of the ring structure formed by bonding adjacent groups to each other include a cyclopentene ring, a cyclohexene ring, a dihydrofuran ring, a dihydropyran ring, a benzene ring, a naphthalene ring, and the like.

R¹～R⁸When being a group other than the group containing the salt-forming group B, is a hydrogen atom, CN, NO₂A hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocycle-containing group having 2 to 20 carbon atoms, but is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and among them, a hydrogen atom or an alkyl group having 1 to 5 carbon atoms is preferable, and a hydrogen atom is particularly preferable. More specifically, as compound A of the present invention, in R⁴In the case of groups containing salt-forming groups, R may preferably be used¹～R³And R⁵～R⁸A compound which is a hydrogen atom. This is because: the compound a of the present invention is excellent in the ease of synthesis, storage stability, solubility in water, and the like.

R¹～R⁸In the case of a group other than the group containing the salt-forming group B, from the viewpoint of improving the absorption efficiency of light in the long wavelength region of the compound A of the present invention, a conjugated system with a three-membered ring is preferably formed, and for example, NO is preferably used₂And an aryl group having 6 to 30 carbon atoms.

R¹⁰¹And R¹⁰²The alkyl group is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms optionally substituted with an alkyl group, an aralkyl group having 7 to 30 carbon atoms optionally substituted with an alkyl group, or a heterocycle-containing group having 2 to 20 carbon atoms, and preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. This is because: the compound a of the present invention is excellent in dispersion stability and ease of synthesis.

Z above¹Is directly bonded,>NR¹⁰¹、>O、>S、>S ═ O or>C ═ O, above Z²Is composed of>CR¹⁰² ₂、>NR¹⁰¹、>O、>S、>S ═ O or>C＝O。

As such Z¹And Z²Preferably comprises a group of¹And Z²The three-membered ring structure of the bonded 2 benzene rings shows a combination of aromaticity. This is because: the compound a of the present invention becomes capable of absorbing light in a wide wavelength region including long-wavelength light.

As the above-mentioned Z¹And the above-mentioned Z²Combinations of (1) include>S and>combinations of C ═ O (thioxanthone structures),>N and>a combination of N (phenazine structure),>N and>combination of ═ O (acridone structure), direct bond and>a combination of ═ O (fluorenone structure), and the like. In the parentheses, the structure of the three-membered ring formed by the above combination is shown.

Among the compounds A of the present invention, the above-mentioned combinations are preferred>S and>the combination of C ═ O (thioxanthone structure), that is, the compound a represented by the general formula (a) in the present invention is a compound represented by the following general formula (a 1). This is because: by bringing Z to¹And Z²The combination of (a) is the above combination, so that the compound a of the present invention becomes easily usable as a radical polymerization initiator more excellent in sensitivity and solubility in water. In addition, Z is¹When directly bonded, Z is contained by 2 benzene rings¹And Z²The ring structure of (2) is a 5-membered ring structure.

Here, in the general formula (A1), R¹、R²、R³、R⁴、R⁵、R⁶、R⁷And R⁸Each independently represents a hydrogen atom, CN, NO₂A hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms optionally substituted with an alkyl group, an aralkyl group having 7 to 30 carbon atoms optionally substituted with an alkyl group, a heterocycle-containing group having 2 to 20 carbon atoms, or a group containing a salt-forming group B represented by the general formula (B1), R¹～R⁸At least one of which is a group comprising a salt-forming group B as described above.

For the general formula (A1)By the use of R¹～R⁸And the general formula (B1) above, showing the same contents as those described in the general formula (a) above.

Specific examples of the compound a of the present invention include the following compounds.

The maximum absorption wavelength of the compound a of the present invention in the range of 300nm to 600nm is preferably 380nm or more, more preferably 385nm to 550nm, particularly preferably 390nm to 500nm, and particularly preferably 390nm to 450nm, as long as it can absorb exposure light and generate radicals. This is because: when the maximum absorption wavelength is in the above range, the compound a of the present invention is more useful as a radical polymerization initiator having excellent sensitivity.

Hereinafter, the method for measuring the maximum absorption wavelength is not particularly limited as long as the maximum absorption wavelength can be measured with good accuracy, and the following method can be used, for example.

(1) Compound a was dissolved in water to prepare an aqueous solution for measurement.

(2) The measurement water solution was filled into a quartz cuvette (optical path length: 10mm, thickness: 1.25mm) and the absorption spectrum was measured using a spectrophotometer (e.g., a visible ultraviolet absorption spectrometer V-670 manufactured by JASCO corporation). The absorption spectrum of the aqueous solution for measurement is an absorption spectrum obtained by subtracting the absorption spectrum of water from the absorption spectrum of the aqueous solution for measurement and correcting the absorption spectrum.

The solubility of the compound a of the present invention with respect to 100 parts by mass of water can be appropriately set according to the use of the compound a of the present invention, and the water-soluble initiator is preferably 0.5 parts by mass or more, more preferably 0.9 parts by mass or more, particularly preferably 1.0 parts by mass or more, particularly preferably 1.2 parts by mass or more, preferably 2.0 parts by mass or more, particularly preferably 3.0 parts by mass or more, particularly preferably 4.0 parts by mass or more, and particularly preferably 5.0 parts by mass or more, from the viewpoint of easy use in a composition containing water. The upper limit of the solubility is preferably higher as the solubility in water is higher, and therefore, the solubility is not particularly limited, but may be 10 parts by mass or less with respect to 100 parts by mass of water, for example.

In addition, the water solubility was set as the following dissolution amounts: in an environmental region at a temperature of 25 ℃ and a Relative Humidity (RH) of 65%, the compound a of the present invention was gradually dissolved until the compound a was no longer dissolved (floating, precipitation, white turbidity was observed) while stirring 100g of deionized water with a stirrer. Specifically, 0.1g of the compound can be added to each of the above solutions to perform the measurement.

As the method for producing compound a of the present invention, any method may be used as long as it can obtain a desired structure, and a known method may be used.

As a method for producing the compound a of the present invention, for example, in the case where the compound a of the present invention has a group of a salt having an acidic group, a known method or a commercially available compound having an acidic group (a carboxylic acid group (-COOH) in the following reaction formula) is prepared as exemplified in the following reaction formula (R1) and reaction formula (R2), and a solution obtained by dissolving the compound in an organic solvent such as dichloromethane or a dispersion obtained by dispersing the compound in an organic solvent such as dichloromethane is prepared.

Next, methods and the like can be mentioned: a method of adding a compound capable of forming a counter cation (a tertiary amine capable of forming a tertiary ammonium cation by hydrogen desorption of a carboxylic acid group in the following reaction formula (R1), and an alcohol solution of an alkali metal hydroxide capable of forming an alkali metal cation in the following reaction formula (R2) (an alcohol solution of KOH)) to the above-mentioned solution or dispersion.

The compound a of the present invention can be used as a radical polymerization initiator that generates radicals by light irradiation, and among these, a water-soluble radical polymerization initiator used for a composition containing water as a solvent is preferably used because the effect of excellent solubility in water can be more effectively exerted.

Specifically, examples of the use of the curable composition using such a radical polymerization initiator include optical materials represented by glasses and photographic lenses, paints, various coating agents, lining agents, inks, resists, liquid resists, adhesives, sealants for liquid crystal dropping methods, image-forming materials, pattern-forming materials, printing plates, insulating varnishes, insulating sheets, laminates, printed circuit boards, sealants for semiconductor devices/LED packages/liquid crystal injection ports/organic ELs/optical elements/electrical insulators/electronic components/separation films, molding materials, electrodes for secondary batteries, separators, putties, building materials, wall boards, glass fiber impregnants, caulking agents, passivation films for semiconductors/solar cells, interlayer insulating films, and the like, Examples of applications include applications to a curable composition that comes into contact with a human body, such as a protective film, a prism lens sheet used for a backlight of a liquid crystal display device, a lens portion of a lens sheet used for a screen of a projection television or the like, a protective film of a liquid crystal color filter, a spacer, a DNA separation chip, a microreactor, a nanobiotechnology device, a recording material for a hard disk, a solid-state imaging device, a solar cell panel, a light-emitting diode, an organic light-emitting device, a light-emitting film, a fluorescent film, a MEMS device, a driver, a hologram, a plasma device, a polarizing plate, a polarizing film, an optical lens such as a microlens, an optical device, an optical connector, an optical waveguide, a casting agent for optical modeling, a dental material, and a nail (nail) application, for example, as a base material that can be applied in the form of a coating agent, examples thereof include metal, wood, rubber, plastic, glass, and ceramic.

Among the applications of the curable composition, from the viewpoint of more effectively exerting the effect of excellent sensitivity, the curable composition is preferably used in an ink application including a member application having a large thickness such as a 3D printing application and a colored photocurable ink application containing a colorant, and from the viewpoint of more effectively exerting the effect of excellent solubility in water, the curable composition is preferably used in a low organic solvent composition application such as a curable composition application in contact with a human body such as a nail art (nail art) application.

B. Free radical polymerization initiator

Next, the radical polymerization initiator of the present invention will be described.

The radical polymerization initiator of the present invention comprises a compound represented by the following general formula (a), i.e., the compound a of the present invention.

Here, in the general formula (A), Z¹Is directly bonded,>NR¹⁰¹、>O、>S、>S ═ O or>C＝O，Z²To represent>CR¹⁰² ₂、>NR¹⁰¹、>O、>S、>S ═ O or>C＝O，R¹、R²、R³、R⁴、R⁵、R⁶、R⁷And R⁸Each independently represents a hydrogen atom, CN, NO₂A hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms optionally substituted with an alkyl group, an aralkyl group having 7 to 30 carbon atoms optionally substituted with an alkyl group, a heterocycle-containing group having 2 to 20 carbon atoms, or a salt-forming group-containing group represented by the following general formula (B1), R¹、R²、R³、R⁴、R⁵、R⁶、R⁷And R⁸At least one of which is a group comprising a salt-forming group B, R¹⁰¹And R¹⁰²Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocycle-containing group having 2 to 20 carbon atoms.

Here, in the general formula (B1), L₁A bonding group representing a direct bond or a b +1 valence; b represents a salt of an acidic group or a salt of a basic group; b represents an integer of 1 to 10; denotes a site bonded to a benzene ring.

The radical polymerization initiator of the present invention contains the compound a of the present invention, and therefore, is excellent in sensitivity and solubility in water.

The radical polymerization initiator of the present invention comprises the compound A of the present invention. The components of the radical polymerization initiator of the present invention are described in detail below.

1. Compound A

The compound A of the present invention is a compound A represented by the above general formula (A). The compound a is the same as that described in the above "a.

The type of the compound a of the present invention may be only 1 type or 2 or more types among radical polymerization initiators. The radical polymerization initiator of the present invention may contain, for example, 2 or more and 5 or less compounds a. For example, in the radical polymerization initiator of the present invention, the compound a of the present invention may include the following two types: compound a having a group containing a salt of an acidic group, and compound a having a group containing a salt of a basic group. The radical polymerization initiator of the present invention may include the following two types: compound a having 1 group containing a salt of an acidic group, and compound a having 2 groups containing a salt of an acidic group.

The content of the compound a of the present invention can be appropriately set depending on the kind of the radical polymerization initiator and the like. The content may be 100 parts by mass in 100 parts by mass of the solid content of the radical polymerization initiator, that is, the radical polymerization initiator of the present invention is composed only of the compound a of the present invention. The content of the compound a of the present invention may be less than 100 parts by mass in 100 parts by mass of the solid content of the radical polymerization initiator, that is, the radical polymerization initiator may be a composition containing the compound a of the present invention and other components, and for example, may be more than 10 parts by mass and 99 parts by mass or less, and preferably 50 parts by mass or more and 95 parts by mass or less. Note that the solid component includes all components except the solvent. This is because: the radical polymerization initiator of the present invention becomes more excellent in sensitivity and solubility in water.

2. Other free radical polymerization initiators

The radical polymerization initiator of the present invention comprises the compound A of the present invention, and may further comprise a radical polymerization initiator compound (hereinafter also referred to as "other initiator compound") other than the compound A of the present invention, if necessary. This is because: by combining another initiator compound with the compound a of the present invention, light in a long wavelength region can be efficiently absorbed, and the radical polymerization initiator of the present invention is more excellent in sensitivity.

In the radical polymerization compound of the present invention, the other initiator compound preferably has solubility in water, and the water solubility is preferably 0.5 parts by mass or more, preferably 1 part by mass or more, particularly preferably 2 parts by mass or more, particularly preferably 10 parts by mass or more, and particularly preferably 30 parts by mass or more, particularly preferably 50 parts by mass or more, per 100 parts by mass of water. This is because: the effect of the compound a of the present invention having excellent solubility in water can be more effectively exhibited. Furthermore, this is because: is useful for aqueous compositions. The upper limit of the solubility is preferably as large as possible, and is not particularly limited, and may be, for example, 1000 parts by mass or less, preferably 300 parts by mass or less.

As such other initiator compounds, any other compounds than the compound a of the present invention may be used, and known radical polymerization initiators may be used. Examples of the other initiator compounds include radical polymerization initiators described in Japanese patent application laid-open No. 2016-176009.

As the other initiator compounds, commercially available products such as N-1414, N-1717, N-1919, PZ-408, NCI-831, NCI-930, and SP-246 (manufactured by ADEKA Co., Ltd.); IRGACURE184, IRGACURE2959, IRGACURE1173, IRGACURE369, IRGACURE907, IRGACURE651, IRGACURE37 379EG, IRGACURE819, IRGACURE754, IRGACURE TPO, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04, IRGACURE127, IRGACURE MBF, IRGACURE500 (manufactured by BASF Corp.); TR-PBG-304, TR-PBG-305, TR-PBG-309, TR-PBG-311, TR-PBG-314, TR-PBG-315, TR-PBG-327, TR-HABI101, TR-HABI 102, TR-HABI 103, TR-HABI 104, TR-HABI 105, TR-HABI 106, TR-HABI 107, TR-OBM, TR-BDK, TR-EDB, TR-EHA, TR-DMB, TR-PTSA, TR-4MBP, TR-BMS, TR-MBF, TR-EMK, TR-NPG, TR-LCV (manufactured by Tronly corporation); SPI-02, SPI-03 (manufactured by Samyang Co., Ltd.), and the like.

Among other initiator compounds, preferred is a compound represented by the following general formula (I) (hereinafter also referred to as "compound I"). This is because: compound I can more effectively exhibit the effect of having excellent solubility in water, and the effect of having excellent solubility in water of compound a of the present invention. Furthermore, this is because: when the compound I is used together with the compound a of the present invention, light in a long wavelength region can be absorbed more efficiently, and the sensitivity is further improved.

Here, in the general formula (I), X¹Represents an aryl group having 6 to 15 carbon atoms, X²Represents a linear alkyl group having 1 to 8 carbon atoms, an alkyl group having 3 to 8 carbon atoms and a branched chain, a linear alkoxy group having 1 to 8 carbon atoms, an alkoxy group having 3 to 8 carbon atoms and a branched chain, or an aryl group having 6 to 15 carbon atoms; a. the^m+A cationic component representing a valence of m; m represents an integer of 1 to 3.

X in the above general formula (I)¹The hydrogen atom in the aryl group having 6 to 15 carbon atoms used may be unsubstituted, but the hydrogen atom is optionally substituted by a straight-chain alkyl group having 1 to 8 carbon atoms, an alkyl group having a branched chain having 3 to 8 carbon atoms, a straight-chain haloalkyl group having 1 to 8 carbon atoms, a halogenated alkyl group having a branched chain having 3 to 8 carbon atoms, a straight-chain alkoxy group having 1 to 8 carbon atoms, an alkoxy group having a branched chain having 3 to 8 carbon atoms, a straight-chain halogenated alkoxy group having 1 to 8 carbon atoms, or a halogenated alkoxy group having a branched chain having 3 to 8 carbon atoms.

Furthermore, X in the formula (I)²Represents a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, a linear alkoxy group having 1 to 8 carbon atoms, a branched alkoxy group having 3 to 8 carbon atoms or an aryl group having 6 to 15 carbon atoms.

X²The hydrogen atom in the aryl group having 6 to 15 carbon atoms used may be unsubstituted, but is optionally substituted with a straight-chain alkyl group having 1 to 8 carbon atoms, a branched-chain alkyl group having 3 to 8 carbon atoms, a straight-chain haloalkyl group having 1 to 8 carbon atoms, a branched-chain haloalkyl group having 3 to 8 carbon atoms, a straight-chain alkoxy group having 1 to 8 carbon atoms, a branched-chain alkoxy group having 3 to 8 carbon atoms, a straight-chain haloalkoxy group having 1 to 8 carbon atoms, a branched-chain haloalkoxy group having 3 to 8 carbon atoms, a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl ether group, a mercapto group, an isocyanate group or a heterocyclic group. X²The methylene groups in the indicated groups are optionally substituted by oxygen or sulfur atoms.

As the above X¹And X²Examples of the aryl group having 6 to 15 carbon atoms to be used include a phenyl group, a trimethylphenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group and the like.

For X as above¹And X²Examples of the linear alkyl group having 1 to 8 carbon atoms used as a substituent for replacing a hydrogen atom thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl.

For X as above¹And X²And a branched alkyl group having 3 to 8 carbon atoms used as a substituent for replacing a hydrogen atom thereof include, for example, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, isopentyl, tert-pentyl, isooctyl, 2-ethylhexyl, and tert-octyl.

For X as above¹And X²And a C1-8 linear haloalkyl group used in place of a substituent for a hydrogen atom thereof, wherein the C1-8 linear alkyl group is a group in which one or more hydrogen atoms are substituted with a halogen atom.

For X as above¹And X²And a branched haloalkyl group having 3 to 8 carbon atoms used in place of a substituent of a hydrogen atom thereof, wherein the haloalkyl group is a group in which one or more hydrogen atoms of the straight-chain alkyl group having 3 to 8 carbon atoms are substituted with a halogen atom.

For X as above¹And X²Examples of the linear alkoxy group having 1 to 8 carbon atoms used in place of the substituent of the hydrogen atom include methoxy group, ethoxy group, n-propoxy group, n-butoxy group, t-butoxy group, n-pentyloxy group, n-hexyloxy group, and n-octyloxy group.

For X as above¹And X²And a branched alkoxy group having 3 to 8 carbon atoms used in place of a substituent of a hydrogen atom thereof include, for example, an isopropoxy group, an isobutoxy group, a cyclobutoxy group, a tert-butoxy group, an isopentyloxy group, a neopentyloxy group, and an isooctyloxy group.

For X as above¹And X²And a C1-8 linear haloalkoxy group used in place of a substituent of a hydrogen atom thereof, wherein the C1-8 linear alkoxy group has one or more hydrogen atoms substituted with a halogen atom.

For X as above¹And X²And a branched haloalkoxy group having 3 to 8 carbon atoms, which is used in place of a substituent of a hydrogen atom thereof, and represents a group in which one or more hydrogen atoms of the linear alkoxy group having 3 to 8 carbon atoms are substituted with a halogen atom.

As the above X¹And X²Halogen atoms as used for the haloalkyl and haloalkoxy groups used, and as substituent X¹And X²Examples of the halogen atom used as a substituent for the hydrogen atom in the group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

In the compounds I according to the invention, X¹Preferred are phenyl, tolyl, xylyl, 2,4, 6-trimethylphenyl and naphthyl. This is because: by making X¹The above-mentioned group is excellent in stability, absorption wavelength and solubility in water of the above-mentioned compound I. Wherein, in the compound I of the invention, X¹2,4, 6-trimethylphenyl is preferred. This is because: the sensitivity of the compound I according to the present invention becomes more excellent.

In the compound I of the present invention, X is as defined above²Aryl groups having 6 to 15 carbon atoms are preferable, and phenyl, tolyl, xylyl, 2,4, 6-trimethylphenyl and naphthyl are preferable. This is because: by making the above-mentioned X²As the above group, the stability, absorption wavelength and solubility in water of the compound I according to the present invention become excellent. Wherein, in the present invention, X is²Preferably phenyl. This is because: the sensitivity of the compound I according to the present invention becomes more excellent.

m represents a number of 1 to 3, and is preferably an integer of 1 to 2, and preferably an integer of 1, from the viewpoint of solubility in water.

A above^m+A cationic component of valency m, capable of reacting withThe acylphosphinic acid forms the counterion. Such a cationic component may be the same as the cationic component described in the section "1. group containing salt-forming group" of the "a. compound" (1) salt of acidic group of (1-1) "of (1) salt-forming group B", for example, as long as the compound I described in the present invention can be provided with desired water solubility.

When the compound a of the present invention contains a salt of an acid group as the salt-forming group B, the above-mentioned cationic component is preferably the same cation as the cationic component constituting the salt of an acid group in the compound a of the present invention. This is because: by using the cationic component, the radical polymerization initiator of the present invention has excellent dispersion stability with less aggregation and precipitation when mixed with, for example, a solvent, a resin, or the like.

In the radical polymerization initiator of the present invention, among them, the cation component is preferably an alkali metal ion, an alkaline earth metal ion or an amine-based cation, particularly preferably an alkali metal ion or a tertiary ammonium cation represented by the above general formula (C3) (cation C3), particularly preferably an alkali metal ion or cation C3, and among them, particularly preferably cation C3. This is because: when the cation component is the cation C3, the sensitivity and solubility in water of the compound I according to the present invention become more excellent. Furthermore, this is because: by combining with the compound a of the present invention, the sensitivity of the radical polymerization initiator of the present invention becomes more excellent.

The content of the other initiator compound may be appropriately set according to the use of the radical polymerization initiator of the present invention, and for example, may be in the range of 1 part by mass or more and 1000 parts by mass or less, preferably 100 parts by mass or more and 800 parts by mass or less, and particularly preferably 200 parts by mass or more and 600 parts by mass or less, relative to 100 parts by mass of the compound a of the present invention.

3. Free radical polymerization initiator

The radical polymerization initiator of the present invention may contain other components in addition to the compound A of the present invention and the other initiator compounds described above. Examples of such other components include those described in "2. radically polymerizable compound", "4. solvent", "5. resin component", and "6. other components" of "c composition" described later. The other components preferably include the non-photosensitive resin described in the above "5. resin component". This is because: the radical polymerization initiator of the present invention is excellent in moldability and storage stability.

The content of the solvent in the radical polymerization initiator of the present invention is preferably small, and for example, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 1 part by mass or less, per 100 parts by mass of the radical polymerization initiator. This is because: the curing treatment of the composition to which the radical polymerization initiator of the present invention is added becomes easy.

As the method for producing the radical polymerization initiator of the present invention, any method may be used as long as the above-mentioned components can be mixed so as to achieve a desired content, and a known mixing method may be used. The radical polymerization initiator of the present invention can be used for, for example, a curable composition which is cured by light irradiation or the like. The specific application of the curable composition may be the same as that described in the above "a compound".

C. Composition comprising a metal oxide and a metal oxide

Next, the composition of the present invention will be described.

The composition of the present invention comprises a compound A represented by the above general formula (A) and a radically polymerizable compound.

This is because: according to the composition of the present invention, by using the compound a of the present invention, a composition having excellent sensitivity and a small content of an organic solvent can be easily obtained. Hereinafter, each component of the composition of the present invention will be described in detail.

1. Compound A

The maximum absorption wavelength of the compound a of the present invention in the range of 300nm to 600nm is preferably 380nm or more, as long as it can absorb exposure light and generate radicals. The more preferable range of the maximum absorption wavelength of the compound a of the present invention may be the same as that described in the above-mentioned item "a.

The content of the compound a in the present invention is not particularly limited as long as it can impart desired curability or the like to the composition. The content may be, for example, 0.05 parts by mass or more and 10 parts by mass or less, and preferably 0.1 parts by mass or more and 5 parts by mass or less, relative to 100 parts by mass of the solid content of the composition. The solid component includes all components except the solvent.

The kind of the compound a of the present invention contained in the composition of the present invention may be only 1 kind, or 2 or more kinds, and may be, for example, 2 or more kinds and 5 or less kinds. The compound a of the present invention may be the same as that described in the section "b. radical polymerization initiator", and therefore, the description thereof will be omitted.

2. Radical polymerizable compound

The radical polymerizable compound in the composition of the present invention has a radical polymerizable group and can be polymerized by a radical. Examples of the radical polymerizable group include an ethylenically unsaturated double bond such as a (meth) acryloyl group, methacryloyl group, and vinyl group. The term (meth) acryloyl is used in a meaning including acryloyl and methacryloyl. In addition, (meth) acrylates are used in the meaning including acrylates and methacrylates.

The radical polymerizable compound in the composition of the present invention may be a compound having an acid value or a compound having no acid value. Examples of the compound having an acid value include a compound having a carboxyl group. When the radical polymerizable compound in the composition of the present invention contains a compound having an acid value, the composition has excellent dispersion stability when it contains water as a solvent.

In addition, the solubility of the light-irradiated portion in the alkaline developer is reduced. Therefore, the composition of the present invention can be used as a photosensitive composition in which the solubility in a solvent such as an alkaline developer changes before and after light irradiation. More specifically, the composition of the present invention can be used as a negative-type composition by containing a compound having an acid value.

As the alkaline developer, an alkaline developer generally used as an alkaline developer, such as a tetramethylammonium hydroxide (TMAH) aqueous solution or a potassium hydroxide aqueous solution, can be used.

Examples of the compound having an acid value include (meth) acrylate compounds having a carboxyl group or the like, such as (meth) acrylic acid.

Examples of the compound having no acid value include (meth) acrylate compounds having no carboxyl group or the like, such as epoxy acrylate resins and 2-hydroxyethyl (meth) acrylate.

In the composition of the present invention, 2 or more kinds of radical polymerizable compounds may be used alone or in combination. For example, as the radical polymerizable compound, a compound having an ethylenically unsaturated double bond group and an acid value and a compound having an ethylenically unsaturated double bond group and having no acid value may be used in combination. When 2 or more kinds of radical polymerizable compounds are mixed and used in the composition of the present invention, they may be copolymerized in advance and used in the form of a copolymer. More specifically, the radical polymerizable compound described in Japanese patent laid-open No. 2016-176009 and the like can be mentioned as such a radical polymerizable compound.

The content of the radical polymerizable compound in the composition of the present invention is not particularly limited as long as a cured product having a desired strength can be obtained, and may be, for example, 10 parts by mass or more and 99 parts by mass or less with respect to 100 parts by mass of the solid content of the composition. This is because: by making the content within the above range, the composition of the present invention can stably hold, for example, the compound a of the present invention.

3. Other free radical polymerization initiators

The composition of the present invention contains the compound A, but may contain a radical polymerization initiator compound (other initiator compound) other than the compound A, if necessary. The contents and types of other initiator compounds may be the same as those described in the section "b. radical polymerization initiator" under "2. other radical polymerization initiators", and therefore, the description thereof will be omitted.

4. Solvent(s)

The composition of the present invention comprises the compound a of the present invention and a radical polymerizable compound, and may further comprise a solvent if necessary. The solvent can disperse or dissolve the respective components of the compound a of the present invention, the radical polymerizable compound, and the like. Therefore, even when the compound is liquid at room temperature (25 ℃) and atmospheric pressure, the compound a and the radical polymerizable compound of the present invention are not contained in the solvent. As the solvent, water or an organic solvent can be used. The solvent preferably contains water from the viewpoints of reducing environmental load, reducing influence on the human body, suppressing dissolution of the organic material when applied to the organic material, and the like.

In the composition of the present invention, the content of water is preferably 50 parts by mass or more, more preferably 80 parts by mass or more, particularly preferably 90 parts by mass or more, and particularly preferably 100 parts by mass, that is, it is preferable that only water is contained as a solvent, in 100 parts by mass of the solvent. This is because: when the water content is in the above range, the composition of the present invention has a reduced environmental burden and a reduced influence on the human body, and is more excellent in the inhibition of the dissolution of an organic material when applied to the organic material.

Examples of the organic solvent usable as the solvent in the composition of the present invention include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; ether solvents such as diethyl ether, dioxane, tetrahydrofuran, 1, 2-dimethoxyethane, 1, 2-diethoxyethane and dipropylene glycol dimethyl ether; ester-based solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and TEXANOL; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, isopropanol or n-propanol, isobutanol or n-butanol, and pentanol; ether ester solvents such as ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether (PGM), propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and ethoxyethyl propionate; aromatic solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane, and cyclohexane; terpene-based hydrocarbon oils such as turpentine, D-limonene and pinene; mineral spirit, Swasol #310 (manufactured by COSMO pine mountain petroleum company, supra); and paraffin solvents such as Solvesso #100 (EXXON chemical Co., Ltd.); halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride and 1, 2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvent, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and the like. The organic solvent is preferably an alcohol solvent from the viewpoint of good compatibility with water.

The content of the solvent in the composition of the present invention may be appropriately set according to the use of the composition of the present invention, and for example, may be 10 parts by mass or more, and preferably 50 parts by mass or more and 95 parts by mass or less, in 100 parts by mass of the composition of the present invention. This is because: the thickness of the coating film can be easily adjusted.

5. Resin component

The composition of the present invention may contain a resin component other than the radical polymerizable compound. Examples of the resin component include polymerizable compounds having a polymerizable group such as a cationic polymerizable compound and an anionic polymerizable compound, and polymers having no polymerizable group.

The content of the resin component is appropriately selected depending on the purpose of use thereof, and is not particularly limited, and may be, for example, 10 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the solid content of the composition. The total content of the resin component and the radical polymerizable compound is appropriately selected depending on the purpose of use thereof, and is not particularly limited, and may be, for example, 10 parts by mass or more and 99 parts by mass or less in total with respect to 100 parts by mass of the solid content of the composition.

(1) Cationically polymerizable compound

In the composition of the present invention, the cationically polymerizable compound may be a compound having 1 or more polymerizable groups capable of cationic polymerization, and a monofunctional compound having 1 or more polymerizable groups and a polyfunctional compound having 2 or more polymerizable groups may be used.

Examples of the cationically polymerizable compound include a compound having a cyclic ether group such as an epoxy compound having an epoxy group and an oxetane compound having an oxetanyl group, and a vinyl ether compound having a vinyl ether group. More specifically, examples of such a cationically polymerizable compound include those described in Japanese patent application laid-open No. 2016-176009. When 2 or more kinds of the cationic polymerizable compounds are used in combination, they may be copolymerized in advance and used in the form of a copolymer. The cationically polymerizable compound can be used together with a cationic initiator such as a photo cationic initiator or a thermal cationic initiator.

(2) Anionic polymerizable compound

In the composition of the present invention, the anionic polymerizable compound may be a compound having 1 or more polymerizable groups capable of anionic polymerization, and a monofunctional compound having 1 or more polymerizable groups and a polyfunctional compound having 2 or more polymerizable groups may be used. Examples of the anionic polymerizable compound include an epoxy compound having an epoxy group, a lactone compound having a lactone group, and a compound having a (meth) acryloyl group.

Examples of the lactone compound include β -propiolactone and caprolactone. As the epoxy compound, the epoxy compounds exemplified as the above cationically polymerizable compound can be used. As the compound having a (meth) acryloyl group, the compounds exemplified as the above radical polymerizable compounds can be used. When 2 or more kinds of the anionic polymerizable compounds are used in combination, they may be copolymerized in advance and used in the form of a copolymer.

(3) Compounds having a photoactive group

In the composition of the present invention, as the polymerizable compound, a compound having a photosensitive group having an unsaturated bond capable of photodimerization (hereinafter, also referred to as "photosensitive group-containing compound") may be used. The photosensitive group and the photosensitive group-containing compound containing the same can be the same as those described in Japanese patent laid-open publication No. 2016-193985.

More specifically, the photosensitive group includes styrylpyridinium (stilbazolium), cinnamoyl, and the like.

The photosensitive group-containing compound is preferably a compound having a hydroxyl group, for example. This is because: the compound having the photosensitive group has excellent solubility in water.

(4) Polymer having no polymerizable group

The polymer has no polymerizable group. Such a polymer may include a repeating structure, and examples thereof include a photosensitive resin having photosensitivity, a non-photosensitive resin having no photosensitivity, and the like.

(4-1) photosensitive resin

The photosensitive resin has photosensitivity, and examples thereof include a normal resin which is used together with an acid generator and changes in a direction of increasing solubility in a developer, such as cutting a chemical bond of an ester group, an acetal group, or the like by an action of an acid. As such a positive resin, for example, a resist base resin or a compound described in japanese patent laid-open publication No. 2016-89085 can be used.

(4-2) non-photosensitive resin

The non-photosensitive resin may be any resin as long as it does not have photosensitivity, and examples thereof include thermoplastic resins such as Polycarbonate (PC), polyethylene terephthalate (PET), polyether sulfone, polyvinyl butyral, polyphenylene ether, polyamide, polyamideimide, polyether imide, norbornene-based resin, acrylic resin, methacrylic resin, isobutylene maleic anhydride copolymer resin, cycloolefin-based resin, polyvinyl alcohol, polyethylene glycol, and polyvinyl pyrrolidone.

As the polyvinyl alcohol, polyvinyl alcohol obtained by polymerizing vinyl alcohol, which is generally called POVAL, partially saponified polyvinyl alcohol, completely saponified polyvinyl alcohol, or a saponified product of a copolymer of vinyl acetate and a monomer having copolymerizability, or the like can be used. Further, modified polyvinyl alcohols obtained by modifying these polyvinyl alcohols with various functional groups can also be used. As the modified polyvinyl alcohol, for example, polyvinyl alcohol having an acetoacetate group as described in Japanese patent application laid-open No. 2009-113347 can be used. As the non-photosensitive resin, a polymer of a polymerizable compound may also be used. That is, the composition of the present invention may be a cured product of a composition containing a polymerizable compound.

(4-3) Polymer

The weight average molecular weight (Mw) of these polymers is appropriately set according to the use of the composition of the present invention, and for example, may be 1500 or more, and may be 1500 or more and 300000 or less. The weight average molecular weight Mw can be obtained as follows: for example, the measurement was performed using HLC-8120GPC manufactured by Tosoh corporation, the elution solvent was N-methylpyrrolidone to which 0.01 mol/L of lithium bromide was added, the calibration curve was Mw377400, 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, and 580 (Easi PS-2 series manufactured by Polymer Laboratories, Inc.) and Mw1090000 (manufactured by Tosoh corporation), and the measurement column was TSK-GELALPHA-M.times.2 (manufactured by Tosoh corporation). The measurement temperature may be set to 40 ℃ and the flow rate may be set to 1.0 mL/min.

6. Other ingredients

The composition of the present invention may contain, in addition to the compound a of the present invention, a radical polymerizable compound, another polymerization initiator, a solvent, and a resin component, other components as needed. Examples of the other components include a cationic polymerization initiator which can be added together with the cationic polymerizable compound or can be added together with the photosensitive compound as an acid generator, and a polymerization initiator such as an anionic polymerization initiator which can be added together with the anionic polymerizable compound.

More specifically, the cationic polymerization initiator described in Japanese patent application laid-open No. 2016-176009 can be used as such a cationic polymerization initiator. Further, as the anionic polymerization initiator and the like, more specifically, a photo-anionic polymerization initiator, a thermal anionic polymerization initiator and the like described in Japanese patent application laid-open No. 2017-073389 are mentioned.

As other components, in addition to the polymerization initiator, additives such as a colorant, an inorganic compound, a colorant, a dispersant for dispersing the inorganic compound and the like, a chain transfer agent, a sensitizer, a surfactant, a silane coupling agent, melamine and the like can be cited.

As the additive, a known material can be used, and for example, a material described in international publication No. 2014/021023 can be used.

The composition of the present invention may contain, in addition to the above-mentioned compounds, salt components such as sodium chloride, potassium chloride, ammonium chloride, sodium acetate, sodium nitrate, lithium chloride, ammonium sulfate, sodium sulfate, lithium sulfate, and potassium sulfate, if necessary. The content of the other components is appropriately selected depending on the purpose of use thereof, and is not particularly limited, and for example, may be 50 parts by mass or less in total with respect to 100 parts by mass of the solid content of the composition.

7. Composition comprising a metal oxide and a metal oxide

As a method for producing the composition of the present invention, any method may be used as long as the above-mentioned components can be mixed so as to achieve a desired content, and a known mixing method may be used. The composition of the present invention can be used as a photocurable composition which is cured by irradiation with light, for example. The specific application may be the same as that described in the above "a. compound".

D. Cured product

Next, the cured product of the present invention will be described.

The cured product of the present invention is a cured product of the composition of the present invention. The cured product of the present invention will be described in detail below. The composition of the present invention may be the same as that described in the above "c composition".

The cured product of the present invention comprises the cured product of the present invention and a polymer containing at least a radical polymerizable compound. The content of the polymer of the radical polymerizable compound may be the same as the content of the radical polymerizable compound described in the above "c.

The cured product of the present invention may be substantially free of a solvent. The content of the solvent contained in the cured product of the present invention may be, for example, 1 part by mass or less, and preferably 0.5 part by mass or less, based on 100 parts by mass of the cured product. This is because: when the content of the solvent is in the above range, the cured product of the present invention has excellent stability with time.

The shape, thickness, and the like of the cured product of the present invention in plan view can be appropriately set according to the use and the like of the cured product of the present invention.

The method for producing the cured product of the present invention is not particularly limited as long as the cured product of the composition of the present invention can be formed into a desired shape. The production method can be the same as that described in "method for producing a cured product" described below, for example, and therefore, the description thereof is omitted.

The use of the cured product of the present invention and the like can be the same as those described in the above "a.

E. Method for producing cured product

Next, a method for producing a cured product of the present invention will be described.

The method for producing a cured product of the present invention includes a step of irradiating the composition of the present invention with light. Hereinafter, each step of the production method of the present invention will be described in detail.

1. Light irradiation step

This step is a step of irradiating the composition of the present invention with light. In this step, the light to be irradiated to the composition of the present invention may be any light that can generate radicals from the compound a of the present invention. The wavelength peak of light is preferably 300nm or more and 500nm or less, more preferably 350nm or more and 500nm or less, particularly preferably 380nm or more and 480nm or less, and particularly preferably 400nm or more and 470nm or less, in order to allow light to sufficiently enter the inside.

The amount of light to be irradiated may be adjusted as long as a cured product having a desired hardness can be formed, and may be adjusted as appropriate according to the coating film thickness of the composition of the present invention. As the light intensity, for example, 10mW/cm may be preferable²Above 300mW/cm²Hereinafter, more preferably 25mW/cm²Above 100mW/cm²Hereinafter, the irradiation time may be preferably 5 seconds to 500 seconds, and more preferably 10 seconds to 300 seconds.

Examples of the light source for light irradiation include ultra-high pressure mercury, mercury vapor arc, carbon arc, xenon arc, and LED light source.

As the light to be irradiated, laser light may be used. The laser light may be laser light including light having a wavelength of 340nm to 430 nm. As the light source of the laser light, a light source emitting light in the visible to infrared region, such as an argon ion laser, a helium neon laser, a YAG laser, or a semiconductor laser, may be used. When these lasers are used, the composition of the present invention may contain a sensitizing dye that absorbs in the visible to infrared region.

In the method for producing a cured product of the present invention, the light irradiation method may be a method of irradiating the entire surface of the coating film of the composition of the present invention in a plan view, or may be a method of irradiating a part of the coating film with light. When the object to be irradiated with light is a part of the coating film, examples of the method of irradiating with light include a method of irradiating with light through a mask or the like, and a method of irradiating only a portion of the composition to be cured with light.

The composition of the present invention may be the same as that described in the above "c composition". The composition of the present invention generally contains a polymerizable compound to form a cured product.

2. Other procedures

The method for producing a cured product of the present invention includes a light irradiation step, and may include other steps as necessary. Examples of the other steps include a step of forming a coating film of the composition of the present invention before the light irradiation step, a development step after the light irradiation step, a step of removing the solvent after the step of forming the obtained coating film, and a heating step (post-baking step) after the light irradiation step. When the composition of the present invention contains a thermal polymerization initiator such as a thermal radical polymerization initiator, a thermal cationic polymerization initiator, or a thermal anionic polymerization initiator, the composition of the present invention may be cured by heating before and after the light irradiation step.

As the step of forming a coating film, any method may be used as long as a coating film of a composition having a desired thickness can be obtained, and known methods such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, and various printing and dipping methods can be used.

The base material for forming the coating film of the composition of the present invention may be appropriately set according to the use of the cured product, and examples thereof include base materials comprising soda glass, quartz glass, semiconductor substrates, metals, paper, plastics, and the like. The cured product may be peeled off from the substrate after being formed on the substrate, or may be transferred from the substrate to another substrate and reused.

As the developing method in the developing step, any method may be used as long as it can remove the uncured composition, and a known developing method such as a method of removing the uncured composition with an alkaline developer may be used.

As a method for removing the solvent in the step of removing the solvent, any method may be used as long as the solvent content in the cured product can be set to a desired amount, and examples thereof include a heating method, that is, a method of performing a prebaking step as the removal step.

The heating temperature in the heating step (post-baking step) performed after the light irradiation step may be set as appropriate depending on the type and use of the cured product, as long as the temperature is a temperature capable of improving the mechanical strength of the cured product.

3. Others

The cured product produced by the method for producing a cured product of the present invention, the use thereof, and the like can be the same as those described in the section "d.

The radical polymerization initiator, the composition containing the same, the cured product thereof, the method for producing the same, and the compound of the present invention are not limited to the above embodiments. The above-described embodiments are illustrative, and embodiments having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same operational effects are included in the technical scope of the present invention.

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